Particulated polyetherimide and method for making

ABSTRACT

Finely divided polyetherimide is provided which can be used in a variety of applications. These oligomers, in the form of fine powders, are particularly useful for coating wire by a power coating technique.

This is a continuation, of application Ser. No. 37,437, filed May 9,1979, now abandoned.

CROSS REFERENCE TO RELATED APPLICATIONS

Reference is made to Banucci et al Ser. No. 788,248, filed Apr. 18,1977, now U.S. Pat. No. 4,098,800, for Process For PreparingPolyetheramide-acids; copending application RD-11113 of Tohru Takekoshifor Polyetherimide Prepolymers and Method for Making, filed concurrentlyherewith; copending application RD-10316 of Tohru Takekoshi for A Methodof Making a Polyetherimide Prepolymer, filed concurrently herewith,where all of the aforementioned applications are assigned to the sameassignee as the present invention.

BACKGROUND OF THE INVENTION

As shown by Banucci et al U.S. Pat. No. 4,098,800, assigned to the sameassignee as the present invention, particulated oligomericpolyetheramide acids can be made by effecting reaction between (a) anaromatic bis(ether anhydride) of the formula, ##STR1## and (b) mixturesof one or more of said bis(ether anhydride)s with up to 30 mole percentbenzophenone dianhydride of the general formula, ##STR2## with at leastone organic diamine of the general formula,

    (3) H.sub.2 N-R-NH.sub.2,

in an inert organic liquid selected from the group consisting of (c)chlorinated hydrocarbon selected from the group consisting of methylenechloride, chloroform, 1,2-dichloroethane, and mixtures thereof and (d)mixtures of said chlorinated hydrocarbon with up to 50% by weight ofacetone to form oligomeric polyetheramide-acid which is substantiallyinsoluble in said liquid, where Z is a member selected from ##STR3## anddivalent organic radicals of the general formula, ##STR4## where X is amember selected from the class consisting of divalent radicals of theformulas,

--C_(y) H_(2y) --, ##STR5## --O-- and --S--, where y is an integer from1 to 5, and R is a divalent organic radical selected from the classconsisting of aromatic hydrocarbon radicals having from 6 to about 20carbon atoms and halogenated derivatives thereof, alkylene radicalshaving from 2 to about 20 carbon atoms, cycloalkylene radicals havingfrom 3 to about 20 carbon atoms, from C₂ to about C₈ alkylene terminatedpolydiorganosiloxane and divalent radicals of the general formula,##STR6## where Q is a member selected from the class consisting of--O--, --S--, and --C_(x) H_(2x) --, where x is an integer from 1 to 5.

It has been found that the above-described particulatedpolyetheramideacids of Banucci et al are useful in various coatingapplications, for example, applications to aluminum or copper wire usingfluid bed electrostatic coating procedures. However, theseelectrostatically applied oligomeric powders can readily form filmscontaining entrapped bubbles which reduce the insulating characteristicsof the polyetherimide coating. It has now been discovered thatsubstantially bubble-free films can be made by preheating theparticulated, substantially organic solvent-free polyetheramide acid,preferably in an oxygen-free atmosphere and at a temperature in therange of 135° C. to 175° C. for a period of time sufficient to effect atleast 70% imidization of the organic solvent-free polyetheramide acidwithout causing a substantial degree of sintering or agglomeration ofthe polyethermide powder. This result is quite surprising since theimidization of the particulated polyetheramide acid occurs in theabsence of an organic solvent.

STATEMENT OF THE INVENTION

There is provided by the present invention, particulated, substantiallyorganic solvent-free polyetherimide having at least 50 mol percent ofimide radicals based on the total mols of imide radicals and amide acidradicals and an average particle size in the range of 0.5 to 70 microns,which is meltable or sinterable at temperatures up to 225° C. andcapable of being converted to a substantially bubble-free flexible filmupon being heated at a temperature in the range of from about 225° C. to325° C. and in substance as high as 400° C.

The particulated polyetherimide of the present invention can be furthercharacterized as being particulated organic solvent-free polyetheramideacid consisting essentially of chemically combined amide acid units ofthe formula, ##STR7## which has been heated at a temperature in therange of about 135° C. to 175° C. until the resulting particulatedproduct consists essentially of about 70 mole percent of chemicallycombined imide units of the formula, ##STR8## where Z and R are aspreviously defined, based on the total moles of chemically combinedimide units and amide acid units without a substantial degree ofsintering occuring in the polyetheramideacid during the aforementionedheat treatment where the polyetheramideacid is the product of reactionof organic dianhydride and organic diamine utilized in a mol ratio of 1mol of organic dianhydride, per 1 to 1.5 mol of organic diamine, wherethe organic dianhydride is selected from the group consisting of

(A) aromatic bis(ether anhydride)s of formula (1) and

(B) mixtures of 1 or more of said bis(etheranhydride)s with up to 30 molpercent of benzophenone dianhydride of formula (2), with at least oneorganic diamine of formula (3), where said polyetheramide acid reactionproduct has a number average molecular weight of below about 5000.

Aromatic bis(ether anhydride)s of formula (1) include, for example:

2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;

4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;

4,4-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;

2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;

4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride

4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;

4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)-diphenyl-2,2-propanedianhydride, and mixtures thereof.

Aromatic bis(ether anhydride)s especially preferred herein are2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride,2,2-bis[4-(2,3-dicarboxyphenoxy)-phenyl]propane dianhydride;4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy) diphenyl-2,2-propanedianhydride; and mixtures thereof.

Some of the aromatic bis(ether anhydride)s of formula (1) are shown inU.S. Pat. No. 3,972,902 (Darrell Heath and Joseph Wirth). As describedtherein, the bis(ether anhydride)s can be prepared from the hydrolysis,followed by dehydration, of the reaction product of a nitro-substitutedphenyl dinitrile with a metal salt of a dihydric phenol compound in thepresence of a dipolar aprotic solvent.

Additional aromatic bis(ether anhydride)s also included by formula (1)are shown by Koton, M. M. Florinski, F. S. Bessonov, M. I. Rudakov, A.P. (Institute of Heteroorganic Compounds, Academy of Sciences,(U.S.S.R.), U.S.S.R. 257,010, Nov. 11, 1969, Appl. May 3, 1967, and byM. M. Koton, F. S. Florinski, Zh, Org. Khin, 4 (5), 774 (1968).

The organic diamines of formula (3) include, for example:

o-phenylenediamine,

m-phenylenediamine,

p-phenylenediamine,

4,4'-diaminodiphenylpropane,

4,4'-diaminodiphenylmethane (commonly named 4,4'-methylenedianiline),

4,4'-diaminodiphenyl sulfide (commonly named 4,4'-thiodianiline),

4,4'-diaminodiphenyl ether (commonly named 4,4'-oxydianiline),

1,5-diaminonaphthalene,

3,3'-dimethylbenzidine,

3,3'-dimethoxybenzidine,

2,4-bis(β-amino-t-butyl)toluene,

bis(p-β-amino-t-butyl)ether,

bis(p-β-methyl-o-aminopentyl)benzene,

1,3-diamino-4-isopropylbenzene,

1,2-bis(3-aminopropoxy)ethane,

benzidine,

m-xylylenediamine,

p-xylylenediamine,

2,4-diaminotoluene

2,6-diaminotoluene,

bis(4-aminocyclohexyl)methane,

3-methylheptamethylenediamine,

4,4-dimethylheptamethylenediamine,

2,11-dodecanediamine,

2,2-dimethylpropylenediamine,

octamethylenediamine,

3-methoxyhexamethylenediamine,

2,5-dimethylhexamethylenediamine,

2,5-dimethylheptamethylenediamine,

3-methylheptamethylenediamine,

5-methylnonamethylenediamine,

1,4-cyclohexanediamine,

1,12-octadecanediamine,

bis(3-aminopropyl)sulfide,

N-methyl-bis(3-aminopropyl)amine,

hexamethylenediamine,

heptamethylenediamine,

nonamethylenediamine,

decamethylenediamine,

bis(3-aminopropyl)tetramethyldisiloxane,

bis(4-aminobutyl)tetramethyldisiloxane, and mixtures of such diamines.

Organic diamines preferred herein are 4,4'-methylenedianiline,4,4'-oxydianiline, metaphenylenediamine, and mixtures thereof.

Benzophenone dianhydrides included by formula (2) include3,3',4,4'-benzophenone tetracarboxylic acid dianhydride,2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, and mixturesthereof. The 3,3',4,4'-isomer is preferred and is referred to herein forsimplicity as BTDA.

In the practice of the invention, particulated oligomeric polyetheramideacids or "polyamide acid" consisting essentially of chemically combinedunits of formula (4), can be heated at temperatures in the range of 135°C. to 175° C. for a period of 1 hour or less to 24 hours or more, basedon the nature of the polyetheramide acid.

As disclosed by Banucci et al, the polyamide acid can be made by usingfrom about 1 to about 1.5 mole of organic diamine, per mole of organicdianhydride. In general, the characteristics of the polyamideacid, i.e.,its ability to be crosslinked for desirable wire coatingcharacteristics, can be influenced by the amine content of the polyamideacid and the nature of the amine.

An alternative procedure for determining whether heat treatment of thepolyamide acid has been sufficient is to titrate the polyamide acidprior to heating and subsequent to the heat treatment, which aspreviously defined, in heating the polyamide acid at a temperature inthe range of 135° C. to 175° C. without sintering the particulate.Preferably, heating is accomplished under a non-oxidizing atmosphere,which can be achieved by using an inert gas such as nitrogen, argon,etc. Residual polyamide acid of less than about 30 mole percent ispreferred, based on the total moles of polyamide acid originallytitrated and can provide oligomer having desirable melt flow propertiesand convertible to bubble-free films.

The amine content, anhydride content and amide acid content of theoligomers prepared in the following examples were determined using thepotentiometric titration procedures next described. Amine content wasdetermined by dissolving a known amount (approximately 0.2 gram) ofsample in 25 cc of liquified phenol (approximately 90 parts phenol and10 parts water) and thereafter titrating with approximately 0.18 Nmethanesulfonic acid dissolved in a mixture of 150 parts by volume ofmethanol and 70 parts by volume of benzene. Amideacid and anhydridecontent were determined by dissolving a known amount (about 0.05 gram)of sample in a mixture of 1 cc water and 2 cc N-methyl-2-pyrrolidone.After allowing one hour for hydrolysis of any anhydride present todicarboxylic acid end groups, 25 cc of pyridine was added and the samplewas titrated with approximately 0.08 N tetrabutylammonium hydroxide(TBAH) prepared by diluting 1 N methanolic TBAH with 100/30 methanolbenzene solution. (The two acid groups derived from the anhydridehydrolysis are stronger and weaker, respectively, than the amideacid).If anhydride was present in the original unhydrolyzed sample, thestronger anhydride-derived carboxylic acid titrates first with a ratherpoorly defined end-point (A). The amide acid titrates next, with awell-defined end point (B). The weaker anhydride-derived carboxylic acidtitrates last, as indicated by a well-defined end point (C) if no imideis present. In such instance, the anhydride content in the originalsample is considered equivalent to the milliequivalents (meq) of baseconsumed from end-point B to end-point C. The amide acid in the sampleis considered equivalent to total base consumed up to end-point B minusthe anhydride content. If imide is present, the end-point for the weakercarboxylic acid is less well-defined because imide ring openingcommences as soon as the weak acid has been neutralized. In thisinstance the choice of end point C is less well-defined and the valuesfor the strong and weak anhydride-derived carboxylic acids are averagedto compute the anhydride content of the original sample. Oligomersprepared at a mole ratio of diamine to dianhydride greater than 1.0 willusually contain no anhydride end groups, and titration of the initialpolyamide acid according to the above procedure will give only one endpoint B from which the milliequivalents of amide acid per gram of samplecan be calculated directly. The amount of imide present, if any, can bedetermined by the procedure described in U.S. Pat. No. 3,892,716 (EdithBoldebuck).

The time and temperature at which a polyamide acid powder can beconveniently heat-treated to produce at least 50% imidization willdepend on the sintering temperature of the sample and also on the amountof amine end groups. Oligomers prepared at higher mole ratio of diamineto dianhydride can be effectively imidized more rapidly and at lowertemperatures than oligomers prepared from equal mole ratios of diamineand dianhydride. To determine a suitable time and temperature forimidization, a polyamide acid powder can be heated for about two hoursat a temperature about 10° to 15° C. lower than the sinteringtemperature. A sample of the heat-treated powder is then titrated todetermine the amide acid content and imide content. The percentimidization is calculated as ##EQU1## If the percent imide in the heatedsample is less than the desired amount, the partially-imidized polyamideacid can be heated further to continue the imidization, using either alonger heating time or by carrying out the imidization at a somewhathigher temperature.

Particle size was measured using the Coulter Counter technique with thepowder suspended in 3 percent aqueous sodium chloride.

In order that those skilled in the art will be better able to practicethe present invention, the following examples are given by way ofillustration and not by way of limitation. All parts are by weight.

EXAMPLE 1

Particulated polyetheramide acid was prepared by the followingprocedure:

A 5% solution of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride (BPADA) was prepared by dissolving 6.50 grams (0.0125 mole)in a sufficient amount of methylene chloride in a first flask. A 5%solution of 4,4'-methylene dianiline (MDA) was prepared by dissolving2.47 grams (0.0125) moles of MDA in a sufficient amount of methylenechloride in a second flask. The BPADA solution and the MDA solution wereadded rapidly and simultaneously with vigorous stirring, at roomtemperature (about 21°-25° C.) to a 500-milliliter breaker, resulting information of a precipitate product within several seconds. Stirring wascontinued for about 10 minutes and thereafter the precipitate productwas separated from the reaction mixture by filtration. The product waswashed with methylene chloride and thereafter dried under vacuum at roomtemperature to provide finely divided free flowing particles. Based onmethod of preparation and titration of the product for amine content,anhydride content, and amide acid content, the product was a lowmolecular weight oligomeric polyetheramide acid adduct of MDA and BPADA,substantially all the end groups of which were amine groups. The numberaverage molecular weight (MW_(n)) of the polyetheramide acid was 2857 ascalculated from the formula: ##EQU2##

Additional particulated polyetheramide acid employing different molratios of BPADA and MDA were also prepared; unlike the above procedure,based on filtering the reaction mixture, the precipitated polyetheramideacid was recovered by removing the solvent under reduced pressure.

The various polyetheramide acid samples were then analyzed formilliequivalents of amine per gram by potentiometric titration withmethane sulfonic acid using phenol:water (90:10) as solvent. The variouspolyetheramide acid samples were then heated to imidize them inaccordance with three different cycles at a temperature of 143° C. for1-4 hours, a temperature of 165° C. for 1-2 hours and at 175° C. for1/2-1 hour. In each heating cycle, the fresh polyetheramide acid powderwas used. The following results were obtained, where "% Imide" indicatesthe initial degree of imidization prior to heating, while "degree ofImidization" shows the extent of how far the particulated polyetheramideacid imidized. The imide content of the oligomer was determined bytitration in accordance with the method of Boldebuck U.S. Pat. No.3,737,478. In addition, the sintering temperatures, i.e., thetemperature at which the powder is converted from the free flowing stateto an agglomerated state of the various polyetheramide acid powders arealso shown.

                                      TABLE I                                     __________________________________________________________________________                            Degree of Imidization (%)                             Composition                                                                           Meq Amine                                                                           Sintering                                                                          Initial                                                                            143° C.                                                                         165° C.                                                                      175° C.                         BPADA:MDA                                                                             per gram                                                                            °C. temp.                                                                   imide %                                                                            1 hr                                                                             2 hr                                                                             4 hr                                                                             1 hr                                                                             2 hr                                                                             1/2 hr                                                                           1 hr                                __________________________________________________________________________    1:1     .08   195  0    13 23 30 24 55 45 64                                  2:3     1.29  165  7    52 82 97 93 98 -- --                                  3:4     .83   185  6    32 44 62 62 96 -- --                                  4:5     .68   195  6    26 36 50 56 92 -- --                                  5:6     .64   195  0    25 36 48 54 83 82 96                                  6:7     .62   195  2    23 34 47 50 82 77 89                                  7:8     .51   195  0    17 30 36 46 78 75 90                                  __________________________________________________________________________

The above results show that amine end group content has a significanteffect on the sintering temperature and on the imidization rate of thepolyetheramide acid.

EXAMPLE 2

A polyetheramide acid was prepared in accordance with the procedure ofExample 1 utilizing equal molar amounts of the BPADA and the methylenedianiline. The resulting particulated organic solvent-freepolyetheramide acid was found to contain 0.19 milliequivalents ofanhydride end groups per gram and 2.37 milliequivalents of amide acidper gram by titration. A portion of the polyetheramide acid was thenimidized utilizing a temperature of 165° C. for a period of 1-4 hours,to serve as a control sample. Additional samples of the polyetheramideacid were also treated with either dimethylamine (B) or trimethyl amine(C) at 25° C. by exposing the polyetheramide acid powder to the aminevapor several times after flushing between each exposure with nitrogenuntil a constant weight was obtained. The amine treated polyetheramideacid powder was also titrated for amine content after the gaseous aminetreatment to consistant weight and then after 4 hours under flowingnitrogen at 165° C. The imidized powders were then converted to films bya melt drawing technique or by being cast from N-methylpyrrolidone andthe resulting film was then cured for 1/2 hour at 300° C. The followingresults were obtained:

                                      TABLE II                                    __________________________________________________________________________                            Extent of                                                                              Cut through*                                                         Imidization, %                                                                         temp of film                                              meq amine per g                                                                          after 165° C.                                                                   cured 1/2 hr                                 Sample       Initial                                                                           4 hrs 165° C.                                                                 1 hr                                                                             2 hr                                                                             4 hr                                                                             300° C.                               __________________________________________________________________________    Control      .29 .16    49 60 69 308°                                  Control + dimethylamine                                                                    2.51                                                                              .49    80 85 85 --                                           (saturated at 25° C.)                                                  Control + trimethylamine                                                                   1.22                                                                              .27    81 87 90 275°                                  (saturated at 25° C.)                                                  __________________________________________________________________________     *Three mil thick film was placed between two crossed noninsulated copper      wires, and tested according to ASTM D1676.                               

The above results establish that the polyetheramide acid can besuccessfully vapor treated in the solid state with a volatile organicamine. In addition, the volatile organic amine treatment enhances therate of imidization.

EXAMPLE 3

In accordance with the procedure of Example 1, additional polyetheramideacid powders were made which were imidized at 165° C. in a nonoxidizingatmosphere for about 2 hours. The imidized powders were then melt drawnon aluminum at about 250° C. and thereafter heated at 300° C. for 1/2hour. The following results were obtained when the cut through wasmeasured under a 1 kilogram load between 50.8 mil crossed wires.

                  TABLE III                                                       ______________________________________                                        Composition   Average                                                         BPADA:MDA     Cut-through Temp.                                                                           Flexibility*                                      ______________________________________                                        1:1           270° C.                                                                              Pass                                              2:3           325° C.                                                                              Borderline                                        3:4            380° C. +                                                                           Pass                                                            345° C.                                                                              Pass                                              4:5            380° C. +                                                                           Pass                                                             380° C. +                                                                           Pass                                              5:5            350° C. +                                                                           Pass                                              6:7            330° C. +                                                                           Pass                                              7:8           310° C.                                                                              Pass                                              ______________________________________                                         *Film was bent and creased.                                              

The above results show that the imidized powder made in accordance withthe present invention can be converted to valuable films which establishthat the powders could also be electrostatically coated onto a copper oraluminum conductor, and can be fused and cured to produce valuableinsulating coatings.

EXAMPLE 4

Polyetheramide acid powder was prepared in accordance with the procedureof Example 1 utilizing BPADA in a mole ratio of one mole of BPADA per1.2 moles of MDA. The resulting organic solvent-free polyetheramide acidpowder was heated under nitrogen for 2 hours at approximately 170° C.The powder was found to be imidized to about 80%. The imidizedpolyetheramide acid was then electrostatically deposited onto a groundedaluminum foil utilizing a negative charged fluidized powder bed. Thepowder coated aluminum foil was then heated for 5 minutes in a 250° C.oven followed by 5 minutes in a 300° C. oven. There was obtained apolyetherimide coated aluminum foil having a cured polyimide film ofabout 5 mils thick free of bubbles and having excellent electricalintegrity.

EXAMPLE 5

The organic solvent-free polyetheramide acid powder prepared in Example4 which had not been heated at 170° C. was spread uniformly onto theflat surface of an aluminum cup. The cup was placed in a 250° C. aircirculating oven and was examined after 5 minutes. The powder had fusedinto a 5 mil film which contained many bubbles and surfaceimperfections. After additional heating at 250° C. for 21/2 hours thefilm still contained many bubbles. The film was found to be completelyunsuitable for electrical insulation purposes.

The above procedure was repeated except that the polyetheramide acid wasimidized under nitrogen for 2 hours at 170° C. There was obtained aparticulated polyetherimide powder which did not show any significantdegree of sintering. The powder was then spread in accordance with theprevious procedure in an aluminum cup and then heated for 5 minutes at250° C. in an air circulating oven. There was obtained a smoothbubble-free film approximately 5 mils in thickness after a period ofabout 5 minutes. The film was then heated for 21/2 hours at 250° C. Thefilm remained smooth and bubble-free and it was found to have adielectric strength at 60 Hertz of about 12.8 kv. This established thatthe imidization in accordance with the method of the present inventionat 2 hours at 170° C. was sufficient to overcome the problem of bubblingwhich characterized the polyetheramide-acid powder heated directly at250° C.

Although the above examples are directed to only a few of the very manyvariables within the scope of the present invention, it should beunderstood that the present invention is directed to a much broadervariety of polyetherimide oligomers and method for making such materialsshown in the description preceding these examples. These polyetherimidepowders can be further characterized in that they can be fused to usefuland bubble-free films without use of external mechanical pressure attemperatures between 200° C. to 250° C. These films can be furtherheated to temperatures up to about 350° C. to flexibilize them.

What we claim as new and desire to secure by Letters Patent of theUnited States is:
 1. A method for making particulated substantiallyorganic solvent-free polyetherimide which comprises heating particulatedsubstantially organic solvent-free polyetheramide acid consistingessentially of chemically combined units of the formula, ##STR9## at atemperature in the range of from 135° C. to 175° C. until the resultingparticulated product consists essentially of at least about 70 molepercent of chemically combined imide units of the formula, ##STR10##based on the total moles of chemically combined imide and amide acidunits without a substantial degree of sintering occurring in theresulting particulated product, where the polyetheramide acid is theproduct of reaction of organic dianhydride and organic diamine utilizedin a mole ratio of 1 mole of organic dianhydride, per 1 to 1.5 mole oforganic diamine, where the organic dianhydride is selected from thegroup consisting of(A) aromatic bis(ether anhydride)s of the formula,##STR11## (B) mixtures of 1 or more of said bis(ether anhydride)s withup to 30 mole percent of benzophenone dianhydride of the formula,##STR12## with at least one organic diamine of the formula,

    H.sub.2 N--R--NH.sub.2,

where said polyetheramide acid reaction product has a number averagemolecular weight of below about 5000,where Z is a member selected from##STR13## and divalent organic radicals of the general formula,##STR14## X is a member selected from the class consisting of divalentradicals of the formulas --C_(y) H₂ y--, --C--, ##STR15## --O--, and--S--, y is an integer from 1 to 5, and R is a divalent organic radicalselected from the class consisting of aromatic hydrocarbon radicalshaving from 6 to about 20 carbon atoms and halogenated derivativesthereof, alkylene radicals having from 2 to about 20 carbon atoms, fromC₂ to about C₈ alkylene terminated polydiorganosiloxane and divalentradicals of the general formula, ##STR16## Q is a member selected fromthe class consisting of --O--, --S--, and --C₂ H_(2x) --, where x is aninteger from 1 to 5.